While photocatalytic oxidations are a category of important reactions in wide chemical synthesis, the fabrication of effective photocatalysts for broad oxidation reactions is still of a great challenge. Herein, by rationally integrating two photochromics, porphyrin and triphenylamine, a three-dimensional photoactive covalent organic framework (COF) is successfully constructed for photocatalytic oxidations. Characterization studies not only show the formation of a crystalline and three-dimensional porous framework, but also reveal its effective photochemical semiconductor properties derived from the porphyrin and triphenylamine moieties. Electron paramagnetic resonance measurements indicate that the COF is an effective photocatalyst for the generation of both singlet oxygen (